CN103076726B - Toner for developing electrostatic latent image, electrostatic charge image developer, toner Cartridge, handle box, imaging device and imaging method - Google Patents

Abstract

The present invention relates to toner for developing electrostatic latent image, electrostatic charge image developer, toner Cartridge, handle box, imaging device and imaging method.Toner of the invention includes toner-particle and external additive, and the average grain diameter of the external additive is of about 70nm to about 420nm, and average roundness is that, less than or equal to about 0.9, and the standard deviation of circularity is more than 0.2.Present invention obtains the toner for developing electrostatic latent image that the generation of wherein pigment figure is inhibited.

Description

Toner for developing electrostatic latent image, electrostatic charge image developer, toner Cartridge, place Reason box, imaging device and imaging method

Technical field

The present invention relates to toner for developing electrostatic latent image, electrostatic charge image developer, toner Cartridge, handle box, into As device and imaging method.

Background technology

JP-A-2005-266557（Patent document 1）A kind of image formation toner is disclosed, it is by least wrapping Add fine inorganic particles and formed in toner-particle outside containing adhesive resin and colouring agent.Wherein, by using wet The fine inorganic particles that method treatment makes the volume distributed median coefficient of variation of size distribution be 50% or smaller are attached to particle of once mixing colours On.

JP-A-2007-199579（Patent document 2）Disclose a kind of toner for developing electrostatic latent image, its by with Lower method is formed：At least adhesive resin and colouring agent are melted, is mediated and is cooled down, gains are ground into particle, and Coarse granule and fine grained are removed by being classified.Wherein, addition circularity be 1.00 to 1.30, average primary particle diameter be 0.05 μm extremely 0.45 μm, and primary particle size standard deviation/average value ratio be 0.25 or smaller fine inorganic particles as external additive.

The content of the invention

It is an object of the invention to provide the toner for developing electrostatic latent image that a kind of generation for making pigment figure is suppressed.

According to the first aspect of the invention, there is provided a kind of toner for developing electrostatic latent image, it includes toner Particle and external additive, the average grain diameter of the external additive is of about 70nm to about 420nm, average roundness be less than or Equal to about 0.9, and the standard deviation of the circularity is more than 0.2.

The second aspect of the invention provides the toner for developing electrostatic latent image according to one side, its Described in the average roundness of external additive be greater than or equal to about 0.5.

The third aspect of the invention provides the toner for developing electrostatic latent image according to one side, its Described in external additive be sol-gel silica.

The fourth aspect of the invention provides the toner for developing electrostatic latent image according to one side, its Described in external additive be to use as the treated sol-gel silica of the organo-silicon compound of hydrophobizers.

According to the fifth aspect of the present invention, there is provided a kind of electrostatic charge image developer, it is included according to first side Toner for developing electrostatic latent image described in face.

According to the sixth aspect of the invention, there is provided a kind of electrostatic charge image developer, it is included according to second side Toner for developing electrostatic latent image described in face.

According to the seventh aspect of the present invention, there is provided a kind of toner Cartridge, it is equipped with according to one side Toner for developing electrostatic latent image, and it can disassemble from imaging device.

According to the eighth aspect of the present invention, there is provided a kind of handle box, it includes developing cell, and can be filled from imaging Put and disassemble, the developing cell includes the electrostatic charge image developer according to the 5th aspect, and utilizes institute Stating electrostatic charge image developer makes the electrostatic image development formed on the surface of image holding member, so as to form toner Image.

According to the ninth aspect of the present invention, there is provided a kind of imaging device, it includes：Image holding member；Charge single Unit, the charhing unit charges to the surface of described image holding member；Electrostatic image forms unit, and it keeps in described image Electrostatic image is formed on the surface of part；Developing cell, the developing cell includes the electrostatic charge according to the 5th aspect Image developer, and make the electrostatic image development using the electrostatic charge image developer, so as to form toner figure Picture；The toner image is transferred to recording medium by transfer printing unit, the transfer printing unit；Cleaning unit, the cleaning unit has Cleaning blade for cleaning the surface of described image holding member；And fixation unit, the fixation unit is by the toner figure As being fixed in the recording medium.

According to the tenth aspect of the present invention, there is provided a kind of imaging method, it includes：To the surface of image holding member Charge；Electrostatic image is formed on the surface of described image holding member；Using the electrostatic charge according to the 5th aspect Image developer makes the electrostatic image development, so as to form toner image；The toner image is transferred to record Medium；The surface of described image holding member is cleaned using cleaning blade；And by the toner image in the note On recording medium.

According to the on one side, be for about 70nm with unused average grain diameter to about 420nm, average roundness be less than or equal to 0.9, and the standard deviation of the circularity is that the situation of external additive more than 0.2 is compared, and being obtained in that makes the generation of pigment figure The toner for developing electrostatic latent image being inhibited.

According to second aspect, compared with the situation of the average roundness less than 0.5 of external additive, wherein color is obtained in that The toner for developing electrostatic latent image that the generation of line is inhibited.

According to the 3rd aspect, compared with the situation of this composition is provided without, the generation that being obtained in that makes pigment figure is pressed down The toner for developing electrostatic latent image of system.

According to the 4th aspect, compared with the situation of this composition is provided without, the generation that being obtained in that makes pigment figure is pressed down The toner for developing electrostatic latent image of system.

According to the 5th aspect, be not used comprising average grain diameter be 70nm to 420nm, average roundness be less than or equal to 0.9, and the circularity standard deviation be external additive more than 0.2 toner for developing electrostatic latent image situation phase Than being obtained in that the electrostatic charge image developer for making the generation of pigment figure be inhibited.

According to the 6th aspect, be not used comprising average grain diameter be 70nm to 420nm, average roundness be less than or equal to 0.9, and the circularity standard deviation be external additive more than 0.2 toner for developing electrostatic latent image situation phase Than being obtained in that the electrostatic charge image developer for making the generation of pigment figure be inhibited.

According to the 7th aspect, be not used comprising average grain diameter be 70nm to 420nm, average roundness be less than or equal to 0.9, and the circularity standard deviation be external additive more than 0.2 toner for developing electrostatic latent image situation phase Than being obtained in that the toner Cartridge for making the generation of pigment figure be inhibited.

According to the 8th aspect, be not used comprising average grain diameter be 70nm to 420nm, average roundness be less than or equal to 0.9, and the circularity standard deviation be external additive more than 0.2 toner for developing electrostatic latent image situation phase Than being obtained in that the handle box for making the generation of pigment figure be inhibited.

According to the 9th aspect, be not used comprising average grain diameter be 70nm to 420nm, average roundness be less than or equal to 0.9, and the circularity standard deviation be external additive more than 0.2 toner for developing electrostatic latent image situation phase Than being obtained in that the imaging device for making the generation of pigment figure be inhibited.

According to the tenth aspect, be not used comprising average grain diameter be 70nm to 420nm, average roundness be less than or equal to 0.9, and the circularity standard deviation be external additive more than 0.2 toner for developing electrostatic latent image situation phase Than being obtained in that the imaging method for making the generation of pigment figure be inhibited.

Brief description of the drawings

Exemplary of the invention is described in detail based on the following drawings, wherein：

Fig. 1 is the figure of the structure of the imaging device for schematically showing exemplary of the invention；And

Fig. 2 is the figure of the structure of the handle box for schematically showing exemplary of the invention.

Specific embodiment

Exemplary of the invention is discussed in detail below.

Toner for developing electrostatic latent image

The toner for developing electrostatic latent image of exemplary of the invention（Hereafter can referred to as " toner "） Comprising toner-particle and external additive, the average grain diameter of the external additive is 70nm to 420nm（Or about 70nm is to about 420nm）, average roundness is less than or equal to 0.9（Or less than or equal to about 0.9）, and the circularity standard deviation be more than 0.2。

The toner of this exemplary has above-mentioned composition, and thus inhibits the generation of pigment figure.

Although not exactly understanding its reason, think that the reason is as follows.

First, in order to prevent external additive from imbedding toner-particle due to mechanical load,

The external additive for having used spherical and diameter big.However, be utilized as toner it is external additive, Circularity can easily pass through cleaning blade close to 1.0 spherical external additive, thus cause the generation of pigment figure.

On the other hand, when external additive is made into irregular shape, the clean-up performance of cleaning blade is improved, And therefore prevent passing through for external additive.

However, when the image of identical patterns is formed continuously using external additive in irregular shape, the image is at this Continuously printed off in the state of sample：In the part that cleaning blade and image holding member contact with each other, toner-particle and outer Portion's additive rests on imaging moiety, but toner-particle and external additive are difficult to rest on non-imaged part.

Therefore, in the part that cleaning blade and image holding member contact with each other, there is toner-particle or outside adds Plus the region of agent may unevenly be distributed on the direction of principal axis of image holding member.As a result, coefficient of friction is generated locally to rise Region high, thus produces pigment figure.

Particularly when in low temperature and low-humidity environment（For example, under 10 DEG C and 10%RH）Under, with low image density（Face Product coverage rate is low）When being formed continuously the image of identical patterns, pigment figure can be substantially produced.

Conversely, in the toner of this exemplary, average grain diameter has been used for 70nm to 420nm, average circle Degree is that, less than or equal to 0.9, and the standard deviation of the circularity is external additive more than 0.2, i.e. circularity is distributed shape wide The irregular external additive of shape.

Herein, circularity is distributed external additive wide and means the big external additive of property in irregular shape, it is specific and Speech, it is intended that comprising from the big particle of property in irregular shape to various external additive particles of the small particle of property in irregular shape External additive.

It is distributed by setting circularity wide, external additive is contained and is moved to from being difficult to be stopped at cleaning blade The external additive of non-imaged part（The small external additive of property in irregular shape）To easily at cleaning blade stop and not Easily mobile external additive（The big external additive of property in irregular shape）Various external additive particles.

That is, it is set smaller than or equal to 0.9 by by the average roundness of external additive, it is suppressed that it passes through cleaning blade Phenomenon, and in the part that cleaning blade is contacted with image holding member, a part of external additive is moved from imaging moiety Move to non-imaged part.Therefore, in the part that cleaning blade and image holding member contact with each other, external additive can be light Change places stop, be unevenly distributed rather than on the direction of principal axis of image holding member.As a result, it is believed that in cleaning blade and image In the part that holding member contacts with each other, on the direction of principal axis of image holding member, it is suppressed that the local elevated area of coefficient of friction The generation in domain.

By this way, the generation of pigment figure is inhibited using the toner of this exemplary.

Using this exemplary toner when, due to what is contacted with each other in cleaning blade and image holding member In part, it is suppressed that the generation in the local elevated region of coefficient of friction, it is taken as that the generation of abnormal sound, cleaning can be suppressed The generation of blade cut and the generation of cleaning blade curling.

The toner of this exemplary is discussed in detail below.

External additive

External additive is described first.

By average grain diameter be 70nm to 420nm, average roundness be less than or equal to 0.9, and the circularity standard deviation External additive more than 0.2 is used as external additive.

Average grain diameter

The average grain diameter of external additive preferably in the range of 70nm to 420nm, more preferably 100nm's to 300nm In the range of, and more preferably in the range of 120nm to 200nm.

When the average grain diameter of external additive is less than 420nm, it is suppressed that the phenomenon that it passs and removes with the time, make outer Portion's additive is easily attached to toner-particle, and inhibits its phenomenon by cleaning blade.

On the other hand, when average grain diameter is more than or equal to 70nm, external additive is difficult in embedment toner-particle.

The average grain diameter of external additive is calculated by the following method：The surface of toner-particle is observed, is observed outside 100 Portion's additive（Particle）, use image processing and analyzing software WinRoof（Manufactured by Mitani Co., Ltd.）Observed by analysis The image on the surface of toner-particle.The average grain diameter of external additive by analyzing the image of primary particle it is meant that obtained Equivalent circle diameter cumulative frequency in 50% diameter（D50v）.

Average roundness

The average roundness of external additive is preferably lower than or equal to 0.9, more preferably less than or equal to 0.85, and more excellent Choosing is less than or equal to 0.80.When the average roundness of external additive is less than or equal to 0.9, being shaped as of external additive is not advised Then, it is and not spherical.It is taken as that, it is suppressed that the phenomenon that external additive passes through cleaning blade, and inhibit color The generation of line.

On the other hand, the average roundness of external additive is preferably greater than or equal to 0.5（Or greater than or equal to about 0.5）, More preferably equal to or greater than 0.60, and more preferably greater than or equal to 0.65.When average roundness is more than or equal to 0.5, outward The aspect ratio of portion's additive is small, therefore external additive not cracky, even if being also such when mechanical load is applied.Therefore, Think due to the fact that and producing the phenomenon of pigment figure to be inhibited：Damaged external additive from（For example）Cleaning blade with The partial exfoliation that image holding member contacts with each other；The hardness of toner-particle is less than the hardness of external additive and is weaker than clear The pressure of clean blade original place movement；And toner-particle is damaged by cleaning blade.

When average roundness is more than or equal to 0.5, it is easy to prepare external additive.

100 external additive particles are observed under 40000 enlargement ratios, and uses image processing and analyzing software WinRoof（Manufactured by Mitani Co., Ltd.）The image on the surface of the toner-particle observed by analysis, thus measures average Circularity.

Circle equivalent girth and girth are calculated by the image analyzed, the circle of each external additive particle is calculated using following formula Degree, and the circularities for averagely being calculated（It is similar to average grain diameter is calculated）.

Circularity=circle equivalent girth/girth=[2 × (A π)^1/2]/PM

In formula, A represents the projected area of each external additive particle, and PM represents each external additive particle Girth.

If circularity is 1.0, mean preferable spheroid.With the reduction of the value, there is bigger inhomogeneities in circumference, And property in irregular shape is uprised.

The standard deviation of circularity

The standard deviation of the circularity of external additive is preferably greater than 0.2, and more preferably greater than 0.22.Herein, by Width is preferably in circularity distribution, therefore the standard deviation of circularity is preferably height.However, when the standard deviation of circularity is too high, circle The different each distribution of particles of angle value is uneven, therefore, the upper limit of the standard deviation of circularity is set to 0.3.

Think that the product of pigment figure can be suppressed by the way that the standard deviation of the circularity of external additive is set greater than into 0.2 It is raw.

The standard deviation of the circularity of external additive is calculated by the circularities of each external additive particle.Specifically, Based on the circularities of the primary particle for being calculated, with the quadratic sum of the difference between the circularities and average roundness of particle divided by Grain sum, calculates the square root of total, as the standard deviation of circularity afterwards.

Material

The advantage of the toner of this exemplary mechanically depends on the mark of average grain diameter, average roundness and circularity Quasi- deviation.Therefore, the material of external additive is not particularly limited, and can be using known material, as long as it meets average The standard deviation of particle diameter, average roundness and circularity.Available external additive material is described below.

Known external additive such as inorganic particle and organic granular are used as external additive.The tool of inorganic particle The example of body includes polytype particle, such as silica（For example, Fumed silica and sol-gel dioxy SiClx), aluminum oxide, titanium oxide, zinc oxide, tin oxide, iron oxide, calcium carbonate, potassium carbonate, tricalcium phosphate and cerium oxide, they It is often used as the external additive of toner surface.The specific example of organic granular includes polytype particle, for example Vinylite, polyester resin, organic siliconresin and fluororesin, they are often used as the external additive of toner surface. In these external additives, sol-gel silica is preferably used.

The method for preparing external additive

An example for preparing the method for external additive is sol-gel process.

Hereinafter, referred to as " sol-gel two will be prepared using the method for preparing external additive of sol-gel process The method of silica ".

The method for preparing sol-gel silica includes, the step of prepare base catalysis agent solution（Hereinafter also referred to as " base catalyst solution preparation step "）, wherein, concentration is contained for the base catalyst of 0.6mol/L to 0.87mol/L is added In having a solvent of alcohol；And during tetraalkoxysilane fed into the base catalysis agent solution, and according to per minute supplied The total amount of tetraalkoxysilane, according to the amount of the base catalyst of every 1 mole of tetraalkoxysilane supply 0.1mol to 0.4mol The step of to feed base catalyst（Hereinafter also referred to as " particle forming step "）.

That is, this preparation method is such method：In the case of the alcohol that there is the base catalyst comprising above-mentioned concentration, While using above-mentioned relation independently supplying tetraalkoxysilane as raw material and base catalyst as catalyst, urge alkalescence Agent reacts to form silica particles with tetraalkoxysilane.

According to this method for preparing sol-gel silica, the generation that can obtain wherein thick agglutinator is suppressed And the low sol-gel silica of circularity.Although the reason for not knowing about definite, but it is believed that its reason is as follows.

First, by preparing base catalysis agent solution（Wherein, during base catalyst is dissolved in the solvent containing alcohol）, and To independently feeding tetraalkoxysilane and base catalyst in the solution so that be fed in base catalysis agent solution four Alkoxy silane reacts, so as to form core particle.Now, when the concentration of the base catalyst in base catalysis agent solution When within the above range, it is believed that inhibit the generation of the thick agglutinator such as example secondary agglutinator, and form the low core of circularity Slug particle.Because, base catalyst has not only played the function of catalyst, its also with the surface of the core particle for being formed Coordination, has shape stability and dispersion stabilization so as to be conducive to core particle.Content base catalysis within the above range Agent heterogeneity it is covered in the surface of core particle（That is, base catalyst is unevenly attached to the surface of core particle）, by This maintains the dispersion stabilization of core particle, but the surface tension and chemical affinity of core particle occur part deviation, from And cause that core particle has low circularity.

By being continually fed into tetraalkoxysilane and base catalyst, the core particle for being formed passes through tetraalkoxysilane Reaction and grow, be derived from silica particles.

Herein, tetraalkoxysilane and base catalyst are fed by with the supply for keeping above-mentioned relation, it is believed that circle The low core particle of degree maintains property in irregular shape in growth, while inhibiting the thick agglutinator such as example secondary agglutinator Produce, thereby produce the sol-gel silica of low circularity.Because, feed tetraalkoxy by with above-mentioned relation Silane and base catalyst, while keeping core particle to disperse, maintain tension force and the chemistry parent on core particle surface With the part deviation of property, thus, core particle maintains property in irregular shape in growth.

Therefore, according to the method for preparing sol-gel silica, the generation that can obtain wherein thick agglutinator is suppressed And the low sol-gel silica of circularity.

Herein, it is believed that the amount of the tetraalkoxysilane for being fed and the size distribution of sol-gel silica or circularity It is relevant.0.0055mol/ (mol minutes) to 0.009mol/ is set in by the amount of the tetraalkoxysilane that will be fed In the range of (mol minutes), can reduce that the tetraalkoxysilane in granular grows step contacts with core particle can Energy property, and before tetraalkoxysilane is uniformly supplied to core particle, cause tetraalkoxysilane and core particle React.I.e., it is believed that, tetraalkoxysilane has preference with the reaction of core particle.Therefore, tetraalkoxy is promoted Silane is provided to inhomogeneities during core particle, so as to result in the inhomogeneous growth of particle.

As a result, such sol-gel silica, the wherein average roundness of sol-gel silica can be produced Less than or equal to 0.9, and property in irregular shape is big, and the standard deviation of its circularity is more than 0.2.

It is additionally considered that the average grain diameter of sol-gel silica depends on the total amount of fed tetraalkoxysilane.

In the method for preparing sol-gel silica, due to foring the core particle with property in irregular shape, And it is maintained property in irregular shape in growth, so as to prepare sol-gel silica, it is taken as that being obtained in that Shape stability is high under mechanical load, and with the sol-gel silica of property in irregular shape.

That is, in the method for preparing sol-gel silica, by the core with property in irregular shape for being formed Particle maintains property in irregular shape in growth, so as to prepare sol-gel silica, it is taken as that be obtained in that can be strong The strong sol-gel silica resisted mechanical load and be difficult to breakage.

In the method for preparing sol-gel silica, by independently by tetraalkoxysilane and base catalyst Feed in base catalysis agent solution, the reaction of tetraalkoxysilane is caused, so as to form particle.Therefore, it is existing with utilization Sol-gel process in technology prepares the silica dioxide granule with property in irregular shape and compares, and can reduce is made The total amount of base catalyst, and therefore can omit the step of removing base catalyst.Work as sol-gel silica When being applied to the product for requiring high-purity, this is favourable.

Base catalyst solution preparation step is described below.

In the preparation process of base catalysis agent solution, the solvent comprising alcohol is prepared, and be added thereto to base catalysis Agent, so as to prepare base catalysis agent solution.

Solvent comprising alcohol can be the only simple solvent comprising alcohol, or can be and such as water, ketone（Such as acetone, MEK and methyl iso-butyl ketone (MIBK)）, cellosolve（Such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and the molten fibre of acetic acid Agent）And ether（Such as diox and tetrahydrofuran）Deng the mixed solvent of other solvents mixing.

In the case of mixed solvent, relative to other solvents, the amount of alcohol is more than or equal to 80 weight %（Preferably greater than or Equal to 90 weight %）.

The lower alcohols such as such as methyl alcohol and ethanol can be used as alcohol.

On the other hand, base catalyst is for promoting tetraalkoxysilane to react（Such as hydrolysis and condensation reaction） Catalyst, and its example include base catalyst, such as ammonia, urea, monoamine and quaternary ammonium salt.In these base catalysts, Ammonia can be preferably used.

The concentration of base catalyst（Content）It is preferred that in the range of 0.6mol/L to 0.87mol/L, more preferably existing In the range of 0.63mol/L to 0.78mol/L, and more preferably in the range of 0.66mol/L to 0.75mol/L.

When the concentration of base catalyst is less than 0.6mol/L, during formed core granular grows are made, core Slug particle it is dispersed unstable, it is thus possible to produce thick agglutinator（Such as secondary agglutinator）, or gel sample may be obtained Shape, thus deteriorates size distribution.

On the other hand, when the concentration of base catalyst is more than 0.87mol/L, the stability mistake of the core particle for being formed Greatly, therefore preferable spherical core particle is formd, thus is difficult to obtain shape of the average roundness less than or equal to 0.90 and does not advise Core particle then.

The concentration of base catalyst means relative to base catalysis agent solution（Base catalyst+the solvent comprising alcohol）It is dense Degree.

Particle forming step is described below.

Particle forming step is such step：Tetraalkoxysilane and base catalyst are independently urged supplied to alkalescence In agent solution, and tetraalkoxysilane is set to be reacted in base catalysis agent solution（Be hydrolyzed reaction and condensation reaction）, So as to prepare sol-gel silica.

In particle forming step, in the initial period of supply tetraalkoxysilane, core particle passes through tetraalkoxy silicon The reaction of alkane and formed（Core particle forming step）, afterwards, core granular grows（Core granular grows step）, thus prepare Sol-gel silica.

Example supplied to the tetraalkoxysilane in base catalysis agent solution includes, tetramethoxy-silicane, tetraethoxy Silane, tetrapropoxysilane and four butoxy silanes.Wherein, from reaction rate controllability, the sol-gel titanium dioxide for being obtained From the point of view of shape, particle diameter, size distribution of silicon etc., it may be preferred to use tetramethoxy-silicane and tetraethoxysilane.

Relative to the alcohol in base catalysis agent solution, the amount of the tetraalkoxysilane supplied is in 0.0055mol/ (mol Minute) in the range of 0.009mol/ (mol minutes).

It means that the alcohol relative to 1mol used in base catalyst solution preparation step, with per minute The speed supply tetraalkoxysilane of 0.0055mol to 0.009mol.

Set within the above range by the amount of the tetraalkoxysilane that will be supplied, can easily prepare average grain diameter Be 70nm to 420nm, average roundness be less than or equal to 0.9, and the circularity standard deviation more than 0.2 external additive.

The particle diameter of sol-gel silica depends on the type or reaction condition of tetraalkoxysilane, however, by inciting somebody to action The total amount of the tetraalkoxysilane for forming reaction for particle for being fed is set as relative to 1L sol-gel silicas point Dispersion liquid is（For example）More than or equal to 0.756mol, it is obtained in that particle diameter is the primary particle more than or equal to 70nm, and lead to Cross the tetraalkoxysilane that will be supplied total amount be set as be relative to 1L sol-gel silica dispersion liquids（For example）It is small In or equal to 4.4mol, primary particle of the particle diameter less than or equal to 420nm is obtained in that.

When the amount of the tetraalkoxysilane supplied is less than 0.0055mol/ (mol minutes), relatively easily prepare point The narrow silica of cloth.

On the other hand, when the amount of the tetraalkoxysilane supplied is more than or equal to 0.009mol/ (mol minutes), Supply excessive for the amount of the tetraalkoxysilane of reaction, and reaction system can be made to be easy to gelation, so as to hinder core The formation of particle or the growth of particle.

The amount of the tetraalkoxysilane supplied is preferably in 0.006mol/ (mol minutes) to 0.0085 (mol minutes) In the range of, and more preferably in the range of 0.006mol/ (mol minutes) to 0.008mol/ (mol minutes).

On the other hand, the example supplied to the base catalyst in base catalysis agent solution includes and same as described above Those.The base catalyst supplied can be and the base catalyst identical being included in advance in base catalysis agent solution Type, or can be the type being different from.The base catalyst of same type can be preferably used.

Relative to every 1mol of the total amount of supplied tetraalkoxysilane per minute, the amount of the base catalyst supplied It is preferred that in the range of 0.1mol to 0.4mol, more preferably in the range of 0.14mol to 0.35mol, and more preferably existing In the range of 0.18mol to 0.30mol.

When the amount of the base catalyst supplied is less than 0.1mol, make the process of formed core granular grows In, core particle it is dispersed unstable, and generate thick agglutinator（Such as secondary agglutinator）, or coagulate reaction system Gel, thus deteriorates size distribution.

On the other hand, when the amount of the base catalyst supplied is more than 0.4mol, the core particle for being formed is excessively steady It is fixed.Therefore, even if when when the low core particle of circularity is formd during forming core particle, making core granular grows During, the core particle for being formed is also with spherical growth, it is thus impossible to often obtain the low sol-gel dioxy of circularity SiClx.

In particle forming step, tetraalkoxysilane and base catalyst are independently supplied to base catalysis agent solution In.However, Supply Method can be method without interruption, or it is interval supply method.

In particle forming step, the temperature of base catalysis agent solution（Temperature during supply）（For example）5 DEG C to 50 DEG C In the range of, and preferably in the range of 15 DEG C to 40 DEG C.

By above-mentioned steps, sol-gel silica is obtained.In this state, the sol-gel two for being obtained Silica has dispersed phase, but therefrom to remove solvent to extract the particle of sol-gel silica.

Removing the example of the method for the solvent in sol-gel silica dispersion liquid includes known method, such as 1） Solvent is removed by filtering, centrifugation, distillation etc., gains is dried using vacuum drier, posture drying machine etc. afterwards Method, and 2）Use the method for the convection drying slurries such as fluid bed dryer, spray dryer.It is not particularly limited and dries temperature Degree, but preferably lower than or equal to 200 DEG C.When drying temperature is higher than 200 DEG C, due to remaining in sol-gel silica table The condensation of the silanol on face, easily causes the combination or coarse grained generation of primary particle.

If desired, removing coarse granule or aggegation from dry sol-gel silica by crushing and sieving Thing.The method of crushing is not particularly limited, but usable drying type pulverizer is carried out, such as airslide disintegrating mill, vibromill, ball mill And needle mill（pin mill）.Sieved using known device, such as vibratory sieve and wind power sieving apparatus.

For the sol-gel silica obtained by using the above-mentioned method for preparing sol-gel silica, can The surface of the sol-gel silica reused after hydrophobization with hydrophobizers.

The example of hydrophobizers includes known with alkyl（Such as methyl, ethyl, propyl group and butyl）It is siliconated Compound.Its specific example includes silicon nitrogen silane compound（For example, such as MTMS, dimethylformamide dimethyl epoxide silicon The silane compounds such as alkane, trim,ethylchlorosilane and trimethylmethoxysilane, HMDS and tetramethylsilazanes）. The combination of one or more in these examples can be used as hydrophobizers.

In these hydrophobizers, the organo-silicon compound with trimethyl group, such as front three can be suitably used Methoxylsilane and HMDS.

The amount of used hydrophobizers is not particularly limited, but for hydrophobization effect, relative to sol-gel dioxy SiClx, preferably in the range of 1 weight of weight % to 100 %, and more preferably in the range of 5 weight of weight % to 80 %.

The method that acquisition had carried out the hydrophobic silica particles dispersion liquid of silicic acid anhydride using hydrophobizers Example include such method：To the hydrophobizers that necessary amounts are added in sol-gel silica dispersion liquid, make gains Reacted within the temperature range of 30 DEG C to 80 DEG C, while being stirred, thus sol-gel silica is carried out at hydrophobization Reason, so as to obtain hydrophobicity sol-gel silica dispersion liquid.When reaction temperature is less than 30 DEG C, it is difficult to carry out hydrophobization Reaction, and when reaction temperature is higher than 80 DEG C, due to self condensation of hydrophobizers, easily cause the gelation of dispersion liquid or molten The aggegation of glue-gel silicas.

On the other hand, obtaining the example of the method for hydrophobicity sol-gel silica particle includes such method, Wherein, hydrophobicity sol-gel silica dispersion liquid is prepared using method as discussed above, side mentioned above is used afterwards Method dries the dispersion liquid, is derived from hydrophobicity sol-gel silica particle；Also include such method, wherein, will be molten Glue-gel silicas dispersion liquid drying is added thereto to hydrophobic with obtaining hydrophily sol-gel silica particle Agent is derived from hydrophobicity sol-gel silica particle to carry out silicic acid anhydride；And including such method, Wherein, the hydrophobicity sol-gel silica dispersion liquid drying that will be obtained is to obtain hydrophobicity sol-gel silica Particle, and hydrophobizers are added thereto to carry out silicic acid anhydride, so as to obtain hydrophobicity sol-gel silica Grain.

The example that the method for hydrophobization is carried out to sol-gel silica particle is such method：Bathed in treatment（Example Such as Henschel blenders or fluid bed）Middle stirring hydrophily sol-gel silica particle, is added thereto to hydrophobization Agent, heats groove so that hydrophobizers gasify, and make the silicon on hydrophobizers and sol-gel silica particle surface Triacontanol group reacts.Treatment temperature is not particularly limited, but for example in the range of 80 DEG C to 300 DEG C, and preferably at 120 DEG C extremely In the range of 200 DEG C.

According to the above-mentioned method for preparing sol-gel silica, it is obtained in that average grain diameter, for 70nm to 420nm, is put down Equal circularity be less than or equal to 0.9, and the circularity external additive of the standard deviation more than 0.2, i.e. circularity distribution is wide , diameter is small and external additive in irregular shape.

Relative to the toner-particle that will be described below of 100 weight portions, 0.5 weight portion to 5.0 weight is preferably added In the range of part, in the range of more preferably 0.7 weight portion to 4.0 weight portions, and more preferred 0.9 weight portion is to 3.5 weight portion models Enclose interior external additive.

Toner-particle

Toner-particle is described below.

Toner-particle comprises at least adhesive resin, and as needed, can further include colouring agent, antitack agent With other internal additives.

Adhesive resin

Adhesive resin is not particularly limited, but its example includes：Homopolymers comprising following monomer, these monomers are（Example Such as）Phenylethylene（Such as styrene, to chlorostyrene and AMS）；Ester with vinyl（Such as acrylic acid first Ester, ethyl acrylate, n-propyl, n-butyl acrylate, lauryl acrylate, 2-EHA, methyl-prop E pioic acid methyl ester, EMA, methacrylic acid n-propyl ester, lauryl methacrylate and methacrylic acid 2- ethyls Own ester）；Vinyl nitrile（Such as acrylonitrile and methacrylonitrile）；Vinyl ethers（Such as methoxy ethylene and vinyl iso-butyl Ether）；Vinyl ketone（Such as methyl vinyl ketone, ethyl vinyl ketone and isopropenyl vinyl ketone）；And polyolefin（Such as second Alkene, propylene and butadiene）, the copolymer comprising two or more these monomers, and their mixture.Its example is also wrapped Include non-vinyl condensation resin, for example epoxy resin, polyester resin, polyurethane resin, polyamide, celluosic resin and poly- Ether resin, the mixture of these resins and vinylite, and vinyl monomer it is common in the presence of be polymerized and The graft polymers of acquisition.

Known method can be applied to single styrenic monomers or (methyl) acrylic ester monomer or application In styrenic monomers and (methyl) acrylic ester combination of monomers, so as to obtain styrene resin, (methyl) acrylic resin With styrene-(methyl) acrylic copolymer resin.Herein, " (methyl) acrylic acid " includes any " acrylic acid " and " first Base acrylic acid ".

Most suitable component is selected from dicarboxylic acid component and diol component, they are combined, and using known Method（Such as ester-interchange method or condensation methods）Synthetic reaction is carried out to gains, so as to obtain polyester resin.

When using styrene resin, (methyl) acrylic resin and its copolymer resin as adhesive resin, preferably , 20,000 to 100, in the range of 000, and number-average molecular weight Mn is 2,000 to 30,000 for weight average molecular weight Mw In the range of.On the other hand, when using polyester resin as adhesive resin, it is preferred that weight average molecular weight Mw 5,000 to In the range of 40,000, and number-average molecular weight Mn is 2,000 to 10, in the range of 000.

The pillar manufactured using the GPC HLC-8120 manufactured by Tosoh Co., Ltd. and by Tosoh Co., Ltd. （TSKgel Super HM-M（15cm））, THF DDGSs are measured with THF solvents, and using by using monodisperse polystyrene Molecular weight calibration curve prepared by alkene standard sample, calculates weight average molecular weight.

The glass transition temperature of adhesive resin is preferably in the range of 40 DEG C to 80 DEG C.By by glass transition temperature Degree is set within this range, and easily keeps minimum fixing temperature.

Will be using differential scanning calorimeter（DSC）And the peak temperature of the endothermic peak for obtaining can be regarded as glass transition temperature.

Colouring agent

Colouring agent is not particularly limited, but known colouring agent can be used.Its example include carbon black, for example furnace black, channel black, Acetylene black, pyrolytic carbon black；Inorganic pigment, such as iron oxide red, barba hispanica and titanium oxide；AZOpigments, such as fast yellow, bisazo Huang, pyrazolone red, chelating are red（chelate red）, bright carmine and pair palm fibre；Phthalocyanine color, such as phthalocyanine blue and without metal Phthalocyanine；And condensation polycyclic pigment, such as flavanthrone is yellow, two bromo anthrones are orange, pyrene is red, quinacridone is red and dioxazine violet.

It is possible if desired to the colouring agent crossed using surface treated, or colouring agent can be made together with dispersant With.Various colorant combinations can be used.

Relative to the gross weight of adhesive resin, the content of colouring agent is preferably in the range of 1 weight of weight % to 30 %.

Antitack agent

The example of antitack agent includes chloroflo；Native paraffin, such as Brazil wax, rice bran wax and candelila wax；Synthesis or ore deposit Thing wax and pertroleum wax, such as lignite wax；And ester type waxes, such as fatty acid ester and montanate.Antitack agent is not limited to these examples.

From from the point of view of storage stability, the fusing point of antitack agent is preferably greater than or equal to 50 DEG C, and more preferably greater than Or equal to 60 DEG C.From it is resistance to it is offset resistance from the point of view of, the fusing point of antitack agent is preferably lower than or equal to 110 DEG C, and more preferably small In or equal to 100 DEG C.

The content of antitack agent preferably in the range of 1 weight of weight % to 15 %, more preferably in the model of 2 weight of weight % to 12 % In enclosing, and more preferably in the range of 3 weight of weight % to 10 %.

Other internal additives

The example of other internal additives includes magnetic material, charge control agent and inorganic powder.

The feature of toner-particle

The feature of toner-particle is described below.

The volume average particle size of toner-particle preferably in the range of 3 μm to 9 μm, and more preferably at 3 μm to 6 μm In the range of.

Using Multisizer-II（Manufactured by Beckman Coulter companies）, volume is measured with 50 μm of pore diameter Average grain diameter.Now, it is scattered in electrolyte aqueous solution by the ultrasonication of 30 seconds or longer time in toner （Isoton solution）In after, measure.

The method for preparing toner

The method of the toner for preparing this exemplary is described below.

Method can be prepared using any dry type（For example mediate comminuting method）Method is prepared with wet type（For example it is coalescence agglutination method, outstanding Floating polymerization, melting suspension comminution granulation, melting suspension method and melting emulsification coalescence agglutination method）Prepare toner-particle.It is not special The method that restriction prepares toner-particle, and known preparation method can be used.

（For example）External additive is added into obtained toner-particle, and is mixed, so as to prepare this example The toner of property embodiment.Mixing（For example）Come by using V-type blender, Henschel blenders and Lodige mixers Carry out.It is possible if desired to remove coarse adjustment toner particles using vibrating screen classifier, wind power sieving apparatus etc..

Electrostatic charge image developer

Electrostatic charge image developer comprises at least the toner of this exemplary.

The electrostatic charge image developer of this exemplary can be the toning only comprising this exemplary The monocomponent toner of agent, or can be comprising the toner being mutually mixed and the two-component developing agent of carrier.

Carrier is not particularly limited, and known carrier can be used.The example of carrier includes carrier, the magnetic of resin coating Property decentralized carrier and resin dispersion type carrier.

In two-component developing agent, the toner of this exemplary and the mixing ratio of carrier（Weight ratio）It is preferred that About 1:100 to about 30:100 toner:In the range of carrier, and more preferably about 3:100 to about 20:100 toner: In the range of carrier.

Imaging device and imaging method

Be described below using this exemplary toner this exemplary imaging device and Imaging method.

The imaging device of this exemplary includes：Image holding member；Charge on surface to image holding member Charhing unit；The electrostatic image that electrostatic image is formed on the surface of image holding member forms unit；Developing cell, Its electrostatic charge image developer for including this exemplary, and make to be protected in image using the electrostatic charge image developer The electrostatic image development formed on the surface of part is held, so as to form toner image；Toner image is transferred to record Transfer printing unit on medium；The cleaning unit of the cleaning blade with the surface for cleaning image holding member；And will adjust The fixing fixation unit on the recording medium of toner image.

In the imaging device of this exemplary, imaging method includes：Surface to image holding member is carried out The charge step of charging；The electrostatic image that electrostatic image is formed on the surface of the image holding member for charging forms step Suddenly；The electrostatic charge for making to be formed on the surface of image holding member using the electrostatic charge image developer of this exemplary Image developing, so as to form the development step of toner image；Toner image is transferred to the transfer step of recording medium；Make The cleaning on the surface of image holding member is cleaned with cleaning blade；And by toner image on the recording medium Fix steps.

When using Electrophtography photosensor as image holding member, according to（For example）In the following manner is in this exemplary reality Apply the formation that image is carried out in the imaging device of scheme.First, using corona charging device or contact type charger by electrofax The surface of photoreceptor is charged, and its exposure is made afterwards to form electrostatic image.Afterwards, make to be formed with developer layer in its surface Developer roll near to or in contact with Electrophtography photosensor so that toner is attached to electrostatic image, thus in electrofax sense Toner image is formed in body of light.The toner image that will be formed using corona charging device etc. is transferred to such as paper or the like The surface of recording medium.Transfer toner image on the surface of the recording medium is fixed device and is fixed, and is thus situated between in record Image is formed in matter.

In the imaging device of this exemplary, it may for example comprise the part of developing apparatus can be can be from imaging The box structure disassembled on device（Toner Cartridge or handle box）.

On toner Cartridge, such toner Cartridge can be suitably used：It includes the quiet of this exemplary Charge image developing toner, and can be disassembled from imaging device.

On handle box, such handle box can be suitably used：It includes developing cell, and is that can be filled from imaging Put what is disassembled, electrostatic charge image developer of the developing cell comprising this exemplary, and utilization should Electrostatic charge image developer makes the electrostatic image development formed on the surface of electrostatic latent image holding member, so as to form toning Agent image.

The example of the imaging device of this exemplary is described below, but imaging device is not limited to the example. Major part shown in figure is described, and does not describe other parts.

Fig. 1 is the schematic diagram of the structure for showing four tandem color imaging devices.Figure 1 illustrates imaging device include the One to the 4th electro photography type image formation unit 10Y, 10M, 10C and 10K（Image formation unit）, their figures according to color separation As data, yellow is exported respectively（Y）, magenta（M）, cyan（C）And black（K）Coloured image.By image formation unit（ Hereinafter referred to as " unit "）10Y, 10M, 10C and 10K are arranged at a predetermined interval in the horizontal direction.Unit 10Y, 10M, 10C Can be the handle box that can be disassembled from the main body of imaging device with 10K.

In figure, in the top of unit 10Y, 10M, 10C and 10K, the intermediate transfer belt 20 as intermediate transfer element prolongs Extend through these units.Intermediate transfer belt 20 is wrapped in the driven roller 22 and support roller contacted with the inner surface of intermediate transfer belt 20 On 24, and run up in the side of the unit 10K from first module 10Y to the 4th, the driven roller 22 and support roller 24 are in figure In be from left to right separated from each other.Using unshowned spring etc., support is oppressed on direction of the support roller 24 away from driven roller 22 Roller 24, thus provides tension force to the intermediate transfer belt 20 being wrapped on the two rollers.The cloth of cleaning device 30 of intermediate transfer element Put in intermediate transfer belt 20 on the surface of image holding member, so as to face driven roller 22.

Yellow in toner Cartridge 8Y, 8M, 8C and 8K, magenta, four kinds of colors of cyan and black can be will be contained in Toner is respectively supplied to the developing apparatus of unit 10Y, 10M, 10C and 10K（Developing cell）4Y, 4M, 4C and 4K.

Because first to fourth unit 10Y, 10M, 10C and 10K has identical structure, therefore, hereafter will be being arranged Upstream on the traffic direction of intermediate transfer belt, and for forming the first module 10Y of yellow image for representative is retouched State.Using corresponding to magenta（M）, cyan（C）And black（K）Rather than yellow（Y）Reference number represent and first module The part identical part of 10Y, and second to the 4th unit 10M, 10C and 10K be not described.

First module 10Y is included as the photoreceptor 1Y of image holding member.Under having been set gradually around photoreceptor 1Y Row part：Charging roller 2Y, the surface of photoreceptor 1Y is charged to predetermined potential by it；Exposure device（Electrostatic image forms unit） 3, its picture signal for being based on color separation is exposed the surface charged using laser beam 3Y, so as to form electrostatic image；Development dress Put（Developing cell）4Y, be fed on electrostatic image powered toner so as to by the electrostatic image development by it；Once Transfer roll（Primary transfer unit）5Y, its toner image that to be developed is transferred on intermediate transfer belt 20；And photoreceptor Cleaning device（Cleaning unit）6Y, there is the removal after primary transfer to remain in the toner on the surface of photoreceptor 1Y for it Cleaning blade 6-1Y.

Primary transfer roller 5Y is arranged on the inner side of intermediate transfer belt 20, and is located at the position relative with photoreceptor 1Y Put.The bias supply of primary transfer bias will be applied（It is not shown）It is connected on primary transfer roller 5Y, 5M, 5C and 5K.Do not showing Under the control of the control unit for going out, bias supply changes and applies to the transfer bias on primary transfer roller.

The operation that yellow image is formed using first module 10Y is described below.Before operation is started, charging roller 2Y is used The surface of photoreceptor 1Y is charged to the current potential of about -600V to about -800V.

Photoreceptor 1Y has a structure in which that wherein photosensitive layer is layered in conducting base（Specific insulation at 20 DEG C It is less than or equal to 1 × 10^-6Ωcm）On.Photosensitive layer has the feature that：Resistance is generally high（With the resistance phase of ordinary resin Together）, but when laser beam 3Y is applied thereto, the resistivity of the part irradiated by laser beam changes.According to from unshowned The yellow image data transmitted in control unit, exposure device 3 exports onto the charging surface of photoreceptor 1Y laser beam 3Y.Swash Light beam 3Y is applied on the photosensitive layer on the surface of photoreceptor 1Y, so that the electrostatic image of yellow printed patterns Formed on the surface of photoreceptor 1Y.

Electrostatic image is the image formed on the surface of photoreceptor 1Y by charging, and is in the following manner The so-called negative sub-image for being formed：The resistivity for making the illuminated part of photosensitive layer using laser beam 3Y is reduced, so that electric charge is in sense Flowed on the surface of body of light 1Y, and electric charge is stayed in the part do not irradiated by laser beam 3Y.

The electrostatic image for being formed on photoreceptor 1Y by this way rotates to predetermined with the rotation of photoreceptor 1Y Developing location.On developing location, the electrostatic image on photoreceptor 1Y is visualized by developing apparatus 4Y（It is changed into development Image）.

For example, being equipped with the electrostatic charge image developer of this exemplary in developing apparatus 4Y, the developer is extremely Contain Yellow toner and carrier less.The Yellow toner is stirred in developing apparatus 4Y, is allowed to be charged by friction, and hold it It is loaded in developer roller（Developer support part）On, the developer roller has the polarity with the electric charge on photoreceptor 1Y（It is negative（-）Pole Property）Identical electric charge.By making the surface of photoreceptor 1Y by developing apparatus 4Y, Yellow toner is by electrostatic adherence in photoreceptor On the surface of 1Y except on electric latent image portion, so as to make image development using Yellow toner.Yellow has been formed on to mix colours The photoreceptor 1Y of agent image continuously runs at a predetermined rate, so as to the developed toner image on photoreceptor 1Y be transmitted To predetermined primary transfer position.

It is when the yellow toner image on photoreceptor 1Y is transported to primary transfer position, predetermined primary transfer is inclined Pressure applies to primary transfer roller 5Y, and the electrostatic force worked towards primary transfer roller 5Y from photoreceptor 1Y is applied to toning Agent image, is thus transferred to intermediate transfer belt 20 by the toner image on photoreceptor 1Y.The transfer bias for now applying have With the polarity of toner（-）Opposite polarity（+）, and the controlled unit in first module 10Y（It is not shown）Regulation and control to about+ 10μA。

On the other hand, remove and reclaim using the cleaning blade 6-1Y of photoreceptor cleaning device 6Y and remain on photoreceptor 1Y Toner.

Similarly control to apply with first module unit to second unit 10M and behind primary transfer roller 5M, Primary transfer bias on 5C and 5K.

Intermediate transfer belt 20（In first module 10Y, yellow toner image is transferred to thereon）Be sequentially transmitted through Second to the 4th unit 10M, 10C and 10K is crossed, thus the toner image of multiple color is able to repeatedly transfer, so as to form folded Plus toner image.

Intermediate transfer belt 20（Four colour toners images are transferred to thereon by Unit first to fourth）Reach secondary turn Print part, support roller 24 and be arranged in that the secondary transfer printing part is contacted by intermediate transfer belt 20 with intermediate transfer belt inner surface Secondary transfer roller on the image bearing side of intermediate transfer belt 20（Secondary transfer unit）26 are constituted.On the other hand, predetermined Time utilization feed mechanism is by recording sheet（Offset medium）P infeeds secondary transfer roller 26 is pressed against each other with intermediate transfer belt 20 and contacts Gap, and predetermined secondary transfer printing bias is applied to support roller 24.The transfer bias for now being applied have and tune The polarity of toner（-）It is identical（-）Polarity, and by the electrostatic force acted on from intermediate transfer belt 20 towards recording sheet P apply to On the toner image of superposition, so as to the toner image of the superposition on intermediate transfer belt 20 is transferred on recording sheet P.This Outward, using resistance detector（It is not shown）The resistance of the second transfer section is detected, secondary transfer printing is determined according to the resistance for being detected Bias, and voltage control is carried out to it.

Afterwards, recording sheet P is fed to fixing device（Roll fixation unit）The compression between a pair of fixing rollers in 28 Part（Retained part）Place, and the toner image that will be superimposed heats the toner image melting so that color addition, and It is fixed to recording sheet P.

Example transferred with the offset medium of toner image is included for electrophotographic copier or printer Common paper and OHP paper.

When after fixing, it is desirable to which when further improving the flatness of imaging surface, the surface of offset medium preferably to the greatest extent may be used Smooth energy, and the use of by the coated paper or copperplate paper of the coatings such as the surface resin of common paper is probably to be especially suitable for 's.

Recording sheet P transferred with coloured image is transported to deliverying unit, thus completes a series of coloured image Form operation.

The imaging device has makes the toner image of superposition be transferred to as recording sheet P by intermediate transfer belt 20 Construction, but it is not limited to this construction.Imaging device can also have wherein toner image to be directly transferred to from photoreceptor The construction of recording sheet.

Handle box and toner Cartridge

Fig. 2 be schematically show the electrostatic charge image developer comprising this exemplary handle box it is suitable Example structure chart.In handle box 200, charging roller 108, developing apparatus 111, the photoreceptor including cleaning blade 113-1 Cleaning device 113, exposure opening 118 and except electricity exposure opening 117 is combined with photoreceptor 107, so that by assembling guide rail 116 form main body.In fig. 2, reference number 300 represents offset medium.

Handle box 200 be can from including transfer device 112, fixing device 115 and other unshowned parts into As being disassembled on apparatus main body.

Handle box illustrated in fig. 2 200 include photoreceptor 107, charging roller 108, developing apparatus 111, cleaning device 113, Expose opening 118 and except electricity exposure opening 117, but can selectively combine these parts.In addition to photoreceptor 107, this example Property embodiment handle box can also include from by charging device 108, developing apparatus 111 and cleaning device（Cleaning unit） 113rd, opening 118 is exposed and except electricity exposes at least one part selected in the groups that opening 117 constitutes.

The toner Cartridge of this exemplary is described below.The toner Cartridge of this exemplary is to include Toner for developing electrostatic latent image and the toner Cartridge that can be disassembled from imaging device.

Imaging device illustrated in fig. 1 is the imaging device having a structure in which, wherein, toner Cartridge 8Y, 8M, 8C and 8K can be disassembled from it.Developing apparatus 4Y, 4M, 4C and 4K by unshowned toner supply pipe with each developing apparatus （Color）Corresponding toner Cartridge is connected.When each toner Cartridge lacks toner, then corresponding toner Cartridge is changed.

Embodiment

This exemplary is described more fully hereinafter with reference to embodiment, but this exemplary is not It is limited to these embodiments.Unless otherwise defined, " part " and " % " is respectively intended to mean " weight portion " and " weight % ".

The preparation of toner-particle 1

The preparation of-particulate resin dispersion 1

Styrene（Produced by Wako Pure Chemical Industries Co., Ltd.）：320 parts

N-BMA（Produced by Wako Pure Chemical Industries Co., Ltd.）：80 parts

β-acryloxypropionic acid（Produced by Rhodia Nicca Co., Ltd.）：9 parts

1', 10- decanediol diacrylate（Produced by Shin Nakamura Chemical Co., Ltd.）：1.5 parts

Dodecanediol（Produced by Wako Pure Chemical Industries Co., Ltd.）：2.7 parts

By 4 parts of anion surfactant Dow Fax（Produced by Dow Chemical companies）It is dissolved in 550 parts of ion exchanges In water, the solution is added thereto and is mixed and is dissolved with the mixture of said components, gains is disperseed and breast in flask Change, will wherein be dissolved with 6 parts of the 50 of ammonium persulfate parts of ion exchange waters and be added thereto, while being slowly stirred and mixing gains 10 Minute.Afterwards, nitrogen displacement is carried out in flask, flask is heated to 70 DEG C using oil bath, while the solution in flask is stirred, and And persistently carry out emulsion polymerization 5 hours, it is derived from the resin anion (R.A.) particle dispersion 1 that solids content is 41%.

The median particle diameter of the resin particle in particulate resin dispersion 1 is 196nm, and glass transition temperature is 51.5 DEG C, And weight average molecular weight Mw is 32400.

The preparation of-particulate resin dispersion 2

Styrene（Produced by Wako Pure Chemical Industries Co., Ltd.）：280 parts

N-butyl acrylate（Produced by Wako Pure Chemical Industries Co., Ltd.）：120 parts

β-acryloxypropionic acid（Rhodia Nicca Co., Ltd.）：9 parts

By 1.5 parts of anion surfactant Dow Fax（Produced by Dow Chemical companies）550 parts of ions are dissolved in hand over Change in water, the solution is added thereto and is mixed and is dissolved with the mixture of said components, gains is disperseed simultaneously in flask Emulsification, will wherein be dissolved with 0.4 part of the 50 of ammonium persulfate parts of ion exchange water and is added thereto, while being slowly stirred and mixing gained Thing 10 minutes.Afterwards, nitrogen displacement is carried out in flask, flask is heated to 70 DEG C using oil bath, while molten in stirring flask Liquid, and persistently carry out emulsion polymerization 5 hours, it is derived from the resin anion (R.A.) particle dispersion 2 that solids content is 42%.

The median particle diameter of the resin particle in particulate resin dispersion 2 is 150nm, and glass transition temperature is 53.2 DEG C, Weight average molecular weight Mw is 41000, and number-average molecular weight Mn is 25000.

The preparation of-coloring agent particle dispersion liquid 1

C.I. the pigment of pigment yellow 74：30 parts

Anion surfactant（Newrex R, are produced by Nippon Oil and Fats Co., Ltd.）：2 parts

Ion exchange water：220 parts

Using homogenizer（ULTRA-TURRAX, is manufactured by IKA companies）By these components mix and carry out it is pre-dispersed, it Ultimaizer is utilized afterwards（Confrontation collision type wet crushing mill, is manufactured by Sugino Machine Limited）, with 245MPa Pressure gains are disperseed 15 minutes, be derived from the median particle diameter of coloring agent particle for 169nm, and solids content is 22.0% coloring agent particle dispersion liquid 1.

The preparation of-anti-sticking agent particle dispersion liquid 1

Solid paraffin HNP 9（75 DEG C of fusion temperature, is produced by Nippon Seiro Co., Ltd.）：45 parts

Cationic surfactant Neogen RK（Produced by Dai-ichi Kogyo Seiyaku Co., Ltd.）：5 parts

Ion exchange water：200 parts

The mixture of these components is heated to 100 DEG C, using homogenizer ULTRA-TURRAX T50（By IKA company systems Make）Disperseed, disperseed using pressure injection type Gaulin homogenizers afterwards, be derived from the intermediate value grain of anti-sticking agent particle Footpath is 196nm, and solids content is 22.0% releasing agent dispersion liquid 1.

Particulate resin dispersion 1：106 parts

Particulate resin dispersion 2：36 parts

Coloring agent particle dispersion liquid 1：30 parts

Anti-sticking agent particle dispersion liquid 1：91 parts

In circular stainless steel flask, using ULTRA-TURRAX T50（Manufactured by IKA companies）Mix these components And disperse, so as to obtain solution.

0.4 part of polyaluminium chloride is added into resulting solution to prepare core agglutinating particle, and it is continuous using ULTRA-TURRAX Gains are disperseed.Solution in flask is stirred, and 49 DEG C are heated to hot oil bath, gains are protected at 49 DEG C Hold 60 minutes, and be added thereto to 36 parts of particulate resin dispersions 1, be thus prepared for core shell agglutinating particle.Afterwards, add 0.5mol/L sodium hydrate aqueous solutions seal stainless steel flask to adjust the pH to 5.6 of solution, molten to gained using magnetic seal Liquid is continuously stirred and is heated to 96 DEG C, and gains are kept for 5 hours, is cooled down afterwards, is derived from yellow Toner-particle.

Will be dispersed in the filtering of the toner-particle in solution and cleaned with ion exchange water, and utilize afterwards Nutsche suction filters carry out solid- liquid separation to it.Gains are dispersed in again in 3L, 40 DEG C of ion exchange water, and with 300rpm is stirred and cleaned 15 minutes.The process 5 times is repeated, when the pH of filtrate is 7.01, electrical conductance is 9.8 μ S/cm, and table When face tension force is 71.1Nm, using Nutsche suction filters, solid- liquid separation is carried out to it using No.5A filter paper, and by gained Solid is dried in a vacuum 12 hours, is derived from the toner-particle that volume average particle size is 6.4 μm.

The preparation of external additive 1

Base catalyst solution preparation step（Base catalysis agent solution（1）Preparation）

Volume is added to be 3L and there is metal stirring rod, drip nozzle 300 parts of methyl alcohol and 47.8 part 10% of ammoniacal liquor（By Teflon（Registration mark）The micro-pipe pump being made）In the glass reaction container of thermometer, and it is stirred and mixes, thus Obtain base catalysis agent solution（1）.Now, base catalysis agent solution（1）In ammonia catalyst amount（NH₃Amount（NH₃[mol]/ （Ammoniacal liquor+methyl alcohol）[L]）It is 0.72mol/L.

Particle forming step（Sol-gel silica dispersion liquid（1）Preparation）

By base catalysis agent solution（1）Temperature adjustment to 25 DEG C, and to base catalysis agent solution（1）Nitrogen is carried out to put Change.Afterwards, in stirring base catalysis agent solution（1）While, 400 parts of tetramethoxies are added dropwise thereto simultaneously by following supply Silane（TMOS）With 260 parts of catalyst（NH₃）Concentration is 4.44% ammoniacal liquor, is derived from sol-gel silica dispersion liquid （Sol-gel silica dispersion liquid（1））.

Relative to base catalysis agent solution（1）The total mole number of middle methyl alcohol, i.e. 0.0059mol/ (mol minutes), by institute The tetramethoxy-silicane of supply（TMOS）Amount be set as 8.4g/ minutes.

Relative to the total amount of supplied tetraalkoxysilane per minute（0.0552mol/ minutes）, by what is supplied The amount of 4.44% ammoniacal liquor is set as 3.97g/ minutes.This amount is relative to the total amount of supplied tetraalkoxysilane per minute Every 1 mole, then equivalent to 0.258mol/ minutes.

The step of making sol-gel silica hydrophobization

5.59 parts of trimethyl silanes are added 200 parts（Solids content is 13.985%）Sol-gel silica dispersion liquid （1）In carrying out silicic acid anhydride.Afterwards, heated at 65 DEG C by using hot plate and dry gains, generated with shape The hydrophobicity sol-gel silica of shape scrambling（1）.

Use hydrophobicity sol-gel silica（1）As external additive 1.

The preparation of external additive 2 to 13

With with prepare the identical mode of external additive 1 and prepare base catalysis agent solution, difference is to be urged in alkalescence In agent solution preparation process, the amount of methyl alcohol and the amount of 10% ammoniacal liquor are substituted with the amount described in table 1.NH₃Amount be documented in table 1 In " NH in 10% ammoniacal liquor₃Amount " in a column.

With with prepare the identical mode of external additive 1 and prepare sol-gel silica dispersion liquid, difference exists In in base catalyst solution preparation process, having used above-mentioned base catalysis agent solution, and replace with the amount described in table 1 In generation, is added to the tetramethoxy-silicane in base catalysis agent solution（TMOS）Amount and the amount of TMOS supplied, and add alkali Catalyst in the ammoniacal liquor of property catalyst solution（NH₃）Concentration, amount and supply.

With with prepare the identical mode of external additive 1, dredged with the sol-gel silica dispersion liquid for being obtained Hydration process and drying process, thus prepare the hydrophobicity sol-gel silica 2 to 13 with property in irregular shape.

Using hydrophobicity sol-gel silica 2 to 13 as external additive 2 to 13.

The amount of the tetramethoxy-silicane in base catalysis agent solution will be added to change into table 1 under " addition total amount " Described value in " weight portion " one column of " TMOS ", and the amount of the tetramethoxy-silicane that will be supplied changes into " confession in table 1 Ying Liang（G/ minutes）" under " TMOS " one column in described value.

The catalyst of the ammoniacal liquor in base catalysis agent solution will be added（NH₃）Concentration change into table 1 " addition total amount " Under " ammoniacal liquor " " NH₃Concentration " value described in a column, the amount of ammoniacal liquor is changed into table 1 under " addition total amount " Described value in " weight portion " one column of " ammoniacal liquor ", and the amount of the ammoniacal liquor that will be supplied changes into " supply in table 1（g/ Minute）" under " ammoniacal liquor " one column in described value.

Here, for the amount of the TMOS for being supplied, by relative to the total mole number of the methyl alcohol in base catalysis agent solution Value be documented in the " supply of table 1（Relative quantity）" under " amount of TMOS " column in.For the amount of the ammoniacal liquor supplied, by phase Value for every 1 mole of the total amount of supplied tetramethoxy-silicane per minute is documented in the " supply of table 1（Relative quantity）" under " NH₃Amount " in a column.

Embodiment 1

The preparation of toner 1

Using Henschel blenders, 2.0 parts of external additives 1 are added into 100 parts of toner-particles 1, thus prepare tune Toner 1.

By the above method toner 1 is carried out graphical analysis as a result, external additive（Sol-gel titanium dioxide Silicon）Average grain diameter be 75nm, average roundness is 0.77, and the circularity standard deviation be 0.21.

The preparation of developer 1

Using V-type blender, 4 parts of toners 1 and 96 parts of carriers hereinafter described are stirred 20 minutes under 40rpm, and And gains are sieved using the sieve that sieve mesh is 250 μm, thus prepare developer 1.

The preparation of carrier 1

Ferrite particles（Average grain diameter is 50 μm）：100 parts

Toluene：14 parts

Styrene-methylmethacrylate copolymer（Component ratio is 90/10）：2 parts

Carbon black（R330, is produced by Cabot companies）：0.2 part

The component in addition to ferrite particles is stirred and disperseed 10 minutes using agitator, so as to prepare coating liquid, will Coating liquid and ferrite particles are added in vacuum outgas kneader, and are stirred 30 minutes at 60 DEG C, are deaerated afterwards and are dried, High-temperature is risen simultaneously and pressure is reduced, and thus prepares carrier 1.

Evaluate

Obtained developer is evaluated in accordance with the following methods.Evaluation result shows in table 2.

Gained developer container is contained in imaging device DocuCentre Color 400（By Fuji Xerox Co. Ltd. systems Make）In.OHP paper is attached to the top of the developing apparatus of imaging device, using every kind of developer, in 10 DEG C, 10%RH（Low temperature And low-humidity environment）In the environment of, printed image on 10,000 A4 paper with 1% image density, to blade curling, it is different The normal generation of noise and the generation of pigment figure are evaluated.Result shows in table 2.

Evaluation to blade curling

Detect by an unaided eye and evaluate the curling of the blade of printing starting stage（Until 100）.Evaluation criterion is as follows.

A：The curling of cleaning blade is not observed.

C：Observation obtains the curling of cleaning blade.

Evaluation to abnormal sound

Abnormal sound on cleaning blade（Pipe）, in the starting stage（After 1 to 10 paper is printed）And in print After 10,000 paper of brush, image holding member is charged and rotate 10 with the processing speed of 194mm/s under non-development state Minute.Afterwards, processing speed is changed into 104mm/s, and evaluates abnormal sound.

Evaluation criterion is as follows.G1, G2 or G3 do not result in any problem in actual applications.

G1：Do not produce abnormal sound.

G2：Piping for small sound is only produced after slow-down, but is disappeared after several paper are printed（This noise level is being beaten Open before imaging device and by ear closer the device when can hear, it is and negligible under normal circumstances）.

G3：Produce piping for small sound（This noise level is being opened before imaging device and ear is moving close to the device When can hear, it is and negligible under normal circumstances）.

G4：Produced in slow-down and piped, and do not disappeared afterwards（This noise level can be heard under normal operation）.

The evaluation of pigment figure

Hereafter, image density is being set as 80% and after printing image on 1000 paper, pigment figure is being commented Valency.

Evaluation criterion is as follows.

A：Produced without pigment figure, and finally obtain good image quality.

B：Slight pigment figure is produced, but just be can be seen by staring, this is allowed level.

C：Due to producing pigment figure, image quality to decline.

Embodiment 2 to 8 and comparative example 1 to 5

Toner and developer are prepared in the same manner as in example 1, and difference is, by the outer of embodiment 1 Portion's additive 1 replaces with the external additive described in table 1, and is commented in the same manner as in example 1 afterwards Valency.Result shows in table 2.

Table 1

Table 2

By the result of table 2 it is known that compared with comparative example, in embodiment 1 to 7, more inhibiting the product of pigment figure The raw, curling of cleaning blade and the generation of abnormal sound.

Compared with comparative example, in embodiment 8, the generation of pigment figure and the generation of abnormal sound are more inhibited.

It is citing and descriptive purpose, has been provided for the foregoing description to exemplary of the invention.Not purport In exhaustion, or limit the invention to disclosed precise forms.It should be apparent to those skilled in the art that many modifications and Modification will be apparent.These embodiments are selected and described in order that principle of the invention and its reality is better described Using so that others skilled in the art understand multiple embodiments of the invention, and its various modification is applicable In desired special-purpose.The scope of the present invention is intended to be limited by appended claims and its equivalents.

Claims (10)

1. a kind of toner for developing electrostatic latent image, comprising：

Toner-particle；With

External additive, its average grain diameter be 70nm to 420nm, average roundness be less than or equal to 0.9, and the circularity mark Quasi- deviation be more than 0.2,

Wherein described average roundness is the value for obtaining in the following manner：

100 external additive particles are observed under 40000 enlargement ratios, and is seen using image processing and analyzing software analysis The image on the surface of the toner-particle examined, circle equivalent girth and girth are calculated by the image analyzed, and calculate every using following formula The circularity of individual external additive particle, and the circularities for averagely being calculated,

Circularity=circle equivalent girth/girth=[2 × (A π)^1/2]/PM

In formula, A represents the projected area of each external additive particle, and PM represents the week of each external additive particle It is long.

2. toner for developing electrostatic latent image according to claim 1, wherein the average roundness of the external additive It is more than or equal to 0.5.

3. toner for developing electrostatic latent image according to claim 1, wherein the external additive is sol-gel Silica.

4. toner for developing electrostatic latent image according to claim 1, wherein the external additive is to use conduct The treated sol-gel silica of the organo-silicon compound of hydrophobizers.

5. a kind of electrostatic charge image developer, comprising toner for developing electrostatic latent image according to claim 1.

6. a kind of electrostatic charge image developer, comprising toner for developing electrostatic latent image according to claim 2.

7. a kind of toner Cartridge, wherein equipped with toner for developing electrostatic latent image according to claim 1, and it can Disassembled from imaging device.

8. a kind of handle box, including developing cell, and it can disassemble from imaging device, and the developing cell includes root According to the electrostatic charge image developer described in claim 5, and made in image maintaining part using the electrostatic charge image developer The electrostatic image development formed on the surface of part, so as to form toner image.

9. a kind of imaging device, including：

Image holding member；

Charhing unit, the charhing unit charges to the surface of described image holding member；

Electrostatic image forms unit, and it forms electrostatic image on the surface of described image holding member；

Developing cell, the developing cell includes electrostatic charge image developer according to claim 5, and using described quiet Charge image developer makes the electrostatic image development, so as to form toner image；

The toner image is transferred to recording medium by transfer printing unit, the transfer printing unit；

Cleaning unit, the cleaning unit has the cleaning blade for cleaning the surface of described image holding member；With

Fixation unit, the fixation unit is by the toner image in the recording medium.

10. a kind of imaging method, including：

Charge on surface to image holding member；

Electrostatic image is formed on the surface of described image holding member；

Make the electrostatic image development using electrostatic charge image developer according to claim 5, so as to form toning Agent image；

The toner image is transferred to recording medium；

The surface of described image holding member is cleaned using cleaning blade；And

By the toner image in the recording medium.